REACTION KINETICS (AS)

 1.Rate of reaction = change in concentration

of reactant or product over time
 Rate of reaction = [reactant]/time OR
[product]/time
 2.Concentration –time graphs

Conc of
a reactant Conc of reactant decreases
with time

time
 Conc of product
increases with
Conc of time
After certain time ,conc of
product products becomes
constant

time
 a. Rate of reaction at time , t :
(instantaneous rate)
 draw a tangent to the concentration
vs time curve at time t
 the gradient of tangent = rate of
reaction
 Example

[reactant ]
Gradient = y/x =
rate of reaction
at time , t

Unit : mol dm-3 s-1 or

y mol dm-3 min-1

t time
 Note :
 i)Average rate : rate measured over a
period of time
 Eg : rate = change in [reactant]/ t2 – t1
 ii)Initial rate : rate at almost t=0
 b. Rate of rxn is proportional to
concentration of most reactants
 Concentration increases, rate increases
 Note : Rate is independent of
concentration of a reactant
 Concentration changes but rate is constant

 Zero order reaction

Conc of Conc decreases with time

reactant Constant gradient
Rate is constant

time
THEORIES OF REACTION
RATES
 1. Collision theory :
 a. reactions occur due to collision of

reactant particles
 b. not all collisions results in reaction

 effective collisions : collisions

between reacting particles that
results in a reaction
c.Characteristics of effective collisions
:
 i) have favourable orientation
 eg C – C – C – C –Br + OH-
 C – C – C – C –OH + Br-
collision of an OH- with the
bromoethane molecule is unlikely to
result in a reaction if it hits the end of
the molecule away from the Br
 ii) possess a minimum energy = Ea
 (1) Definition : Activation energy ,Ea,
is the minimum energy required for a
reaction to take place
 High Ea  slow reaction

 (2) Ea is used to enable bonds in the

reactants to stretch and break as new
bonds form in the products
 2. Transition state theory :
 a. reactions takes place via transition
state in which reactants come together
 b. bond making and breaking occur
continuously and simultaneously
 In the transition state, bonds are in the
process of making and breaking.
  A-B + C  A + B-C

 A B C
Bond breaking transition state Bond forming
 c. reaction profile/enthalpy diagram :
 Note :

 (1) Transition state is the highest

point in the reaction profile
 (2) Energy gap between reactants and
transition state = Ea
 (3) Ea forward rxn ≠ Ea reverse rxn
 Reaction profile or energy / enthalpy
diagram for uncatalysed reactions

 exothermic reversible reaction

Transition state
Energy

Ea forward rxn
Ea reverse rxn

Reactants H

Products

Extent of reaction
 endothermic reversible reaction

Transition state
Energy
Ea reverse rxn
Ea forward rxn

Products
H

Reactants

Extent of rxn
d. Multi step reaction

 Reaction that takes place via an

intermediate
 Mechanism of rxn involves a multi
step reaction
 The intermediate will occur at a
minimum on the graph
 One minimum = one intermediate
Eg :
Step 1 : Reactants  Intermediate ,
H = positive
Step 2 : Intermediate  Products ,
H = negative

Overall : Reactants  Products ,

H = negative
 Transition state 1
Transition state 2
Energy
Ea(1) Ea (2)

Intermediate

Reactants
Overall H

Products

Extent of rxn
 e. Reacting particles must possess
energy greater than or equal to the Ea
before they can react
FACTORS AFFECTING
RATE OF REACTION
 Concentration

 Temperature

 Catalyst
 I. Concentration of reactants
 1. conc increases , rate normally
increases
 ( exception : zero order )

 2. as concentration increases :

 frequency of collisions increases

 no of effective collisions increases
 rate of reaction increases
 3. Expt to show effect of concentration on
rate of reaction :
 Eg:
 Na2S2O3(aq) + 2HCl(aq)  2 NaCl(aq) +
H2O(l) + SO2(g) + S(s)
 a. Effect of [S2O32-] on rate of reaction
 b. Sulphur appears as particles of solid
 c. Measure time taken to block view of
cross/words under conical flask
 Experiment to show effect of concentration
on rate of reaction :
 Eg Na2S2O3 (aq) + 2HCl (aq) 
2 NaCl(aq) + H2O(l) + SO2(g) + S(s)
a. Effect of conc of S2O32- on rate of rxn
b. Sulphur appears as small particles of
solid
c. Measure time taken for enough sulphur to
form to block view of the cross/words
under conical flask
 d. Use different volumes of S2O32- but
keep volume of HCl constant
 e. H2O used to keep total volume of all
mixtures constant
 Hence volume of S2O32- used  conc
S2O32-
 eg : volume doubles , conc doubles
Mixture Volume of Volume of Volume of Time/s
S2O32-/cm3 HCl/cm3 H2O/cm3

1 10 20 30

2 20 20 20

3 40 20 0
 Rate of reaction α 1/time
 From expt ,
 As volume of S2O32- increases,
 [S2O32-] increases , time taken
decreases
 Rate of reaction increases
 Rate of reaction α [S2O32-]

1 / time

[S2O32- ]
II.Temperature
 1. When temperature increases :
 average speed of reacting particles
increases
 particles collide more frequently and
with greater energy
 no of particles with energy ≥ Ea
increases
 no of effective collisions increases
 rate of reaction increases
 2. Why does rate increase with
temperature?
 Molecules in a gas does not all have the
same speed.
 Their speeds and therefore their
energies are distributed according to the
Maxwell Boltzmann distribution curve
  Maxwell Boltzmann distribution curve

Fraction or no of
molecules with
energy E

Most probable energy

Energy/speed
 a. Shape : at a temp T , molecules in
a sample of gas have different
speed/energy
 Most probable speed/energy
corresponds to the maximum of the
curve.
 b. Area under the curve = total no of

molecules in the sample

 c. As temp increases ,
 curve flattens ( have a lower peak )

 more spread out ( moves to the right )

 however total no of molecules =

areas under the curves remains the

same
  Effect on Maxwell Boltzmann distribution curve

No of molecules
with energy E Lower T
Higher T

Ea Energy/speed
 d. Shaded area = no of molecules with
energy ≥ Ea
 As temp increases ,
 Size of shaded area increases
 More molecules with energy ≥ Ea
 No of effective collisions increases
 Rate of reaction increases
 Note : At temp T and ( T + 10 K ) ,
 Size of shaded area doubles
 No of molecules with energy ≥ Ea
doubles
 Rate of reaction doubles
 e. Reactions with larger Ea are slower
but rise in temp has more
significant increase on the rate of
reaction with a higher Ea
 III.Effect of catalyst ( catalysis )

 1.Catalysts are substances that affects the

rate of a chemical reaction without being
chemically changed themselves
 They are not consumed and are
regenerated at the end of the reaction
 Properties of catalyst:
 increase the rate of reaction
 amount of catalyst used affects the rate
which is proportional to the amount used
 required in small amount
 chemically unchanged after the reaction
 do not affect H
 2. Two types of catalyst :
 a. positive catalyst : increases rate of
reaction
eg ferum in Haber process
 b. negative catalyst / inhibitor : slows
down a reaction
eg glycerine or phosphoric acid
inhibits decomposition of hydrogen
peroxide
 3. Action of positive catalyst
 Provides alternative pathway with a
lower Ea
 More molecules with energy ≥ Ea
 No of effective collisions increases
 Rate of reaction increases
 Note : different catalyst can affect a
similar reaction differently
 4. Diagrams :
a. Enthalpy diagram or energy profile :
eg exothermic rxn

Energy
Ea uncatalysed rxn

Ea catalysed rxn(lower)

Reactants

Products

Reaction pathway
 b. Maxwell Boltzmann distribution curve
( at a certain temp T )

No of molecules
with energy E

Ea uncatalysed Energy
Ea catalysed (lower)
 For catalysed reaction :
 Size of shaded area increases
 No of molecules with energy ≥ Ea
increases
 No of effective collisions increases
 Rate of reaction increases
 Note : another factor affecting rate is
surface area ( higher surface area ,
faster reaction )
 5. Types of catalyst : 3 types
 a. Heterogeneous catalyst : catalyst is in a different
phase compared to reactants .
 Examples :
 Reaction Catalyst
 N2(g) + 3H2(g)  2NH3(g) ferum (s)
( Haber process )
2SO2(g) + O2(g)  2SO3(g) V2O5 (s)
( Contact process )
C2H4(g) + H2(g)  C2H6(g) Ni (s)
( Hydrogenation of alkenes in
manufacture of margarine )
 b. Homogeneous catalyst : catalyst is present in the
same phase as the reactants.
 Examples:
 Reaction Catalyst
 CH3COOH(aq) + C2H5OH(aq) H+ (aq)
 CH3COOC2H5(l) + H2O (l)

S2O82- (aq) + 2I- (aq) Fe2+(aq)

 2SO42- (aq) + I2 (aq) or Fe3+ (aq)
 c. Biological catalyst ( enzymes ):
 Proteins which catalyses chemical reactions in living
systems
 Are extremely specific , one enzyme normally
catalyses one reaction
 Example: amylase found in saliva. It is used to break
carbohydrates into simpler molecules.
Autocatalysis
 1. One of the product is a catalyst for the
reaction
 2. Reaction proceeds slowly at first at
uncatalysed rate
 until a significant amount of the product (
also the catalyst ) is established
 3. Then reaction will speed up to catalysed
rate
 Reaction will stop when reactants are
exhausted
 Eg :
 2 MnO4- + 16 H+ + 5 C2O42- 

2 Mn2+ + 8 H2O + 10 CO2

catalyst
 Slow decrease in conc
Slow reaction

[ MnO4- ] Uncatalysed rate

Fast decrease in
conc
Faster reaction
Catalysed rate

time
rate
Fast
Catalysed rate

Slow
Uncatalysed
rate

time